KR20200132710A - Sun screen composition comprising a complex formation of bis-ethylhexyloxyphenol methoxyphenyl triazine - Google Patents

Abstract

Disclosed in the present specification is a water-in-oil type ultraviolet light-blocking composition which comprises: microparticles containing a polymer matrix in which bis-ethylhexyloxyphenol methoxyphenyl triazine is dispersed; and bis-ethylhexyloxyphenol methoxyphenyl triazine dissolved in a polar oil, in combination in an oil phase part. Compared to a composition which comprises microparticles containing the polymer matrix in which bis-ethylhexyloxyphenol methoxyphenyl triazine is dispersed, or bis-ethylhexyloxyphenol methoxyphenyl triazine dissolved in a polar oil alone, the present invention exhibits a further improved ultraviolet light blocking effect while containing a smaller amount of bis-ethylhexyloxyphenol methoxyphenyl triazine, and can provide a fresh sensation of use without stickiness.

Description

Sun screen composition comprising a complex formation of bis-ethylhexyloxyphenol methoxyphenyl triazine}, including bis-ethylhexyloxyphenol methoxyphenyl triazine

The present specification describes a composition having excellent UV blocking efficiency.

Cross-reference to related applications

This application claims priority to Korean Patent Application No. 10-2019-0057115 filed on May 15, 2019, the entire contents of which are incorporated herein by reference.

Ultraviolet (UV) has been identified as a major cause of skin erythema, swelling, and freckles, and extremely skin cancer, and many studies on various skin diseases caused by UV rays are being conducted. In general, ultraviolet rays are classified into a UV-C wavelength of 240 to 280 nm, a UV-B wavelength of 280 to 320 nm, and a UV-A wavelength of 320 to 400 nm, depending on the wavelength. Of these, UV-C passes through the ozone layer and disappears without reaching the surface, UV-B penetrates to the epidermis of the skin, causing erythema, freckles, and swelling, and UV-A penetrates to the dermis of the skin to form wrinkles and melanin. It is known to cause back skin aging and skin irritation or skin cancer.

With the recent increase in the amount of UV irradiation on the surface due to the destruction of the ozone layer, the market for products primarily aimed at UV protection is growing every year, and consumers' needs for a composition for UV protection over the entire wavelength range are increasing. .

In general, a composition for UV protection has been proposed in a W/O (Water in Oil) type with oil as the trauma or an O/W (Oil in Water) type with water as trauma. In the case of the O/W type, the feeling of use when applied to the skin has a refreshing advantage compared to the W/O type product, but it still has the disadvantage of being easily washed away by sweat or water despite continuing research to improve water resistance. , It has the disadvantage that the persistence of the UV blocking effect is remarkably poor. On the other hand, in the case of W/O type, it has excellent durability compared to O/W type products, but it has a disadvantage of being heavy and sticky in use, which is not irrelevant to the high viscosity of general W/O type products. In addition, the W/O-type product has a disadvantage in that the emulsion stability is lower than that of the O/W-type because it is manufactured with high viscosity by increasing the ratio of the water phase, which is the inner merchant, to lightly control the feeling of use. On the contrary, W/O-type products with low viscosity have a problem in that the stability of the product is deteriorated due to the separation of the water phase as the inner and the oil phase (oil phase) as the outer when stored for a long time in a container during distribution. Therefore, in order to increase the stability, the viscosity is increased, and when the viscosity is increased, the feeling of use becomes heavy and sticky.

Bis-ethylhexyloxyphenol methoxyphenyl triazine is an effective organic UV blocker that can effectively block UVA and UVB at the same time, but other organic UV rays that can dissolve BEMT due to its poor solubility in solvents. It had to be applied to the oil phase by dissolving in a barrier agent or oil having a high polarity. Therefore, there was a limitation that it was difficult to apply bis-ethylhexyloxyphenol methoxyphenyl triazine to products of various formulations. In addition, when bis-ethylhexyloxyphenol methoxyphenyl triazine is applied to the composition, the feeling of use is very greasy and sticky, so it is difficult to provide a product that can be applied lightly and neatly as required by consumers.

Korean Patent Publication No. 10-1773095

In one aspect, the problem to be solved by the present invention is to provide a composition that contains a small amount of bis-ethylhexyloxyphenol methoxyphenyl triazine and has excellent UV protection efficacy and a fresh and light feeling of use.

In one aspect, the present invention comprises an aqueous phase and an oil phase, the oil phase, bis-ethylhexyloxyphenol methoxyphenyl triazine (Bis-ethylhexyloxyphenol methoxyphenyl triazine) microparticles comprising a polymer matrix comprising a dispersed polymer matrix; And bis-ethylhexyloxyphenol methoxyphenyl triazine dissolved in polar oil, W/O (Water in Oil) type UV protection composition is provided.

In one aspect, the present invention comprises microparticles comprising a polymer matrix in which bis-ethylhexyloxyphenol methoxyphenyl triazine is dispersed and bis-ethylhexyloxyphenol methoxyphenyl triazine dissolved in polar oil together, skin Bis-ethylhexyloxyphenol methoxyphenyl triazine is mixed and applied in the form of microparticles and dissolved in oil, so that it is more evenly distributed on the skin. Therefore, the present invention is less than a composition comprising microparticles comprising a polymer matrix in which bis-ethylhexyloxyphenol methoxyphenyl triazine is dispersed, or a composition comprising bis-ethylhexyloxyphenol methoxyphenyl triazine alone dissolved in a polar oil. While including bis-ethylhexyloxyphenol methoxyphenyl triazine, it exhibits a more improved UV blocking effect, and can provide a refreshing feeling without being sticky.

1A is a SEM (Scanning Electrom Microscopy) image of bowl-shaped microparticles according to an embodiment of the present invention.
1B is an image of a high magnification of the same sample as in FIG. 1A.
FIG. 2 is a diagram showing observation results of Example 2/Example 5/Example 3/Example 4/Comparative Example 2 at week 4 (cold and hot storage) sequentially from the left.
3 is a diagram showing the observation results of Example 2/Example 5/Example 3/Comparative Example 2/Example 4 at week 4 (room temperature storage) sequentially from the left.
4 is a view showing the observation results of Comparative Example 2 / Example 5 / Example 4 / Example 2 / Example 3 in order from the left at the 8th week (refrigerated storage after 4 weeks of cold and hot).
5 is a diagram showing observation results of Comparative Example 2/Example 5/Example 4/Example 2/Example 3 at week 8 (room temperature storage) sequentially from the left.
6 is a view showing the observation results of Comparative Example 2 / Example 5 / Example 4 / Example 2 / Example 3 in order from the left at the 9th week (4 weeks cold and hot + 4 weeks frozen + room temperature storage).
7 is a diagram showing the observation results of Comparative Example 2 / Example 5 / Example 4 / Example 2 / Example 3 sequentially from the left during long-term storage (4 weeks cold and hot + 4 weeks frozen + 1 year room temperature storage) .

Hereinafter, exemplary embodiments of the present application will be described in more detail with reference to the accompanying drawings. However, the technology disclosed in the present application is not limited to the embodiments described herein and may be embodied in other forms. However, the embodiments introduced herein are provided so that the disclosed content may be thorough and complete, and the spirit of the present application may be sufficiently conveyed to those skilled in the art. In addition, those of ordinary skill in the relevant field will be able to implement the spirit of the present application in various other forms within the scope of the technical spirit of the present application.

In one embodiment, the present invention relates to a W / O (Water in Oil) type UV-blocking composition comprising an aqueous portion and an oil phase. In one embodiment, the oil phase portion is microparticles comprising a polymer matrix in which bis-ethylhexyloxyphenol methoxyphenyl triazine is dispersed; And bis-ethylhexyloxyphenol methoxyphenyl triazine dissolved in polar oil.

Another embodiment is a microparticle comprising a polymer matrix in which bis-ethylhexyloxyphenol methoxyphenyl triazine (Bis-ethylhexyloxyphenol methoxyphenyl triazine) is dispersed for use in the preparation of a UV blocking composition; And bis-ethylhexyloxyphenol methoxyphenyl triazine dissolved in polar oil, wherein the composition is a W/O (Water in Oil) type composition including an aqueous phase and an oil phase, and the bis -Microparticles comprising a polymer matrix in which ethylhexyloxyphenol methoxyphenyl triazine is dispersed; And bis-ethylhexyloxyphenol methoxyphenyl triazine dissolved in polar oil may be included in the oil phase. Another embodiment is a microparticle comprising a polymer matrix in which bis-ethylhexyloxyphenol methoxyphenyl triazine is dispersed; And bis-ethylhexyloxyphenol methoxyphenyl triazine dissolved in polar oil in an effective amount to a target in need thereof, wherein the bis-ethylhexyloxyphenol Microparticles comprising a polymer matrix in which methoxyphenyl triazine is dispersed; And bis-ethylhexyloxyphenol methoxyphenyl triazine dissolved in polar oil may be included and applied to the oil phase of the W/O type composition including an aqueous phase and an oil phase. Another embodiment is a microparticle comprising a polymer matrix in which the bis-ethylhexyloxyphenol methoxyphenyl triazine is dispersed as an active ingredient for use in a sunscreen composition; And bis-ethylhexyloxyphenol methoxyphenyl triazine dissolved in polar oil, wherein the composition is a W/O type composition comprising an aqueous phase and an oil phase, and the bis-ethylhexyloxyphenol methoxy Microparticles comprising a polymer matrix in which phenyl triazine is dispersed; And bis-ethylhexyloxyphenol methoxyphenyl triazine dissolved in polar oil may be included in the oil phase. As an embodiment, the use may be a non-therapeutic use.

Other chemical names of bis-ethylhexyloxyphenol methoxyphenyl triazine included in the present invention are 2,4-bis[4-(2-ethylhexyloxy)-2-hydroxyphenyl] -6-(4-methoxyphenyl)-1,3,5-triazine, also called bemotriniol, and its CAS registration number is 187393-00-6. As an example, the bis-ethylhexyloxyphenol methoxyphenyl triazine may be sold as Tinosorb S® from BASF. The bis-ethylhexyloxyphenol methoxyphenyl triazine is known as an organic sunscreen that can block UVA and UVB at the same time, but has low solubility and has been provided in a state dissolved in polar oil or prepared in the form of microparticles. . However, when provided in a state dissolved in polar oil, it is difficult to include in a large amount in the composition due to the heavy and sticky feeling of use, so there is a problem that a satisfactory UV blocking effect cannot be exhibited. Even if it is provided in the form of microparticles, it has no choice but to contain only a small amount due to precipitation problems.When applied to the skin, even if it is evenly applied to the skin, the uncoated part occurs, so there is a problem that a satisfactory UV blocking effect cannot be obtained. have. On the other hand, the present invention includes a raw material stabilizing bis-ethylhexyloxyphenol methoxyphenyl triazine in polymer microparticles and a small amount of bis-ethylhexyloxyphenol methoxyphenyl triazine dissolved in polar oil, -Ethylhexyloxyphenol Methoxyphenyl Triazine is mixed in the skin and applied to the skin without any gaps, thereby maximizing UV protection.

As an example, the bis-ethylhexyloxyphenol methoxyphenyl triazine of bis-ethylhexyloxyphenol methoxyphenyl triazine dissolved in the polar oil may be included in an amount of 0.01 to 2% by weight based on the total weight of the composition. When the bis-ethylhexyloxyphenol methoxyphenyl triazine is included in an amount of less than 0.01% by weight based on the total weight of the composition, the UV protection effect is insignificant, and when it exceeds 2% by weight, the content of polar oil is also high, so it is sticky and heavy. Appears, there is a problem that it is not suitable for producing a composition having a light feeling of use such as the W/S type. Specifically, the composition comprises bis-ethylhexyloxyphenol methoxyphenyl triazine of bis-ethylhexyloxyphenol methoxyphenyl triazine dissolved in polar oil, 0.01% by weight or more, 0.05% by weight or more, based on the total weight of the composition, 0.1% or more, 0.2% or more, 0.3% or more, 0.4% or more, 0.5% or more, 0.6% or more, 0.7% or more, 0.8% or more, 0.9% or more, 1.0% or more, 1.1% by weight or more, 1.2% by weight or more, 1.3% by weight or more, 1.4% by weight or more, 1.5% by weight or more, 1.6% by weight or more, 1.7% by weight or more, 1.8% by weight or more, or 1.9% by weight or more. In addition, the composition contains bis-ethylhexyloxyphenol methoxyphenyl triazine dissolved in polar oil, based on the total weight of the composition, 2.0 wt% or less, 1.9 wt% or less, 1.8 wt% or less, 1.7 wt% or less, 1.6 wt% Below, 1.5% by weight or less, 1.4% by weight or less, 1.3% by weight or less, 1.2% by weight or less, 1.1% by weight or less, 1.0% by weight or less, 0.9% by weight or less, 0.8% by weight or less, 0.7% by weight or less, 0.6% by weight It may contain below, 0.5% by weight or less, 0.4% by weight or less, 0.3% by weight or less, 0.2% by weight or less, 0.1% by weight or less, 0.05% by weight or less, or 0.02% by weight or less.

As an example, the polar oil in which the bis-ethylhexyloxyphenol methoxyphenyl triazine is dissolved is not precipitated even when bis-ethylhexyloxyphenol methoxyphenyl triazine is stored for a long period of time and can be provided in a stably dissolved state. If it is, it is not limited to the type and can be included in all. The polarity of oil is determined according to the presence, type, number of functional groups in each oil, or the structure of the substance. Typically, alcohols, esters, vegetable oils having a linear structure having a hydrophilic functional group The lights are classified as oils with relatively high polarity. For example, the polar oil may include an oil containing at least one polar functional group of a carboxyl group (-COO), a ketone group (-CO), and a hydroxy group (-OH). Specifically, the polar oil is butylene glycol dicaprylate*dicapriate, ethylhexyl salicylate, ethylhexyl methoxycinnamate, homosalate, C12-15 alkyl benzoate, dibutyl adipate, dicaprylyl Carbonate, caprylyl-caprylate, coco caprylate, octocrylene, propylheptyl caprylate, isopropyl palmitate, caprylic/capric triglyceride and coco glyceride. More specifically, the polar oil may include one or more of butylene glycol dicaprylate*dicapriate, C12-15 alkylbenzoate, and dicaprylyl carbonate, and the oil is less heavy than other polar oils. It exhibits a high solubility in bis-ethylhexyloxyphenol methoxyphenyl triazine while being wet.

As an embodiment of the present invention, microparticles comprising a polymer matrix in which bis-ethylhexyloxyphenol methoxyphenyl triazine is dispersed may be included in an amount of 0.1 to 30% by weight based on the total weight of the composition. When the microparticles are included in an amount of less than 0.1% by weight based on the total weight of the composition, the UV blocking effect is insignificant, and when it exceeds 30% by weight, the microparticles, that is, the powder formulation, may be excessively included, resulting in a frustrating feeling of use. Specifically, the composition comprises 0.1% by weight or more, 0.5% by weight or more, 1.0% by weight or more, 2.0% by weight or more, 3.0% by weight or more, 4.0% by weight or more, 5.0% by weight or more, based on the total weight of the composition, 6.0% or more, 7.0% or more, 8.0% or more, 9.0% or more, 10% or more, 11% or more, 12% or more, 13% or more, 14% or more, 15% or more, 16% or more, 17% or more, 18% or more, 19% or more, 20% or more, 21% or more, 22% or more, 23% or more, 24% or more, 25% or more, It may include at least 26% by weight, at least 27% by weight, at least 28% by weight, or at least 29% by weight. In addition, the composition comprises 30% by weight or less, 29% by weight or less, 28% by weight or less, 27% by weight or less, 26% by weight or less, 25% by weight or less, 24% by weight or less based on the total weight of the composition. Wt% or less, 22 wt% or less, 21 wt% or less, 20 wt% or less, 19 wt% or less, 18 wt% or less, 17 wt% or less, 16 wt% or less, 15 wt% or less, 14 wt% or less, 13 Wt% or less, 12 wt% or less, 11 wt% or less, 10 wt% or less, 9 wt% or less, 8 wt% or less, 7 wt% or less, 6 wt% or less, 5 wt% or less, 4 wt% or less, 3 It may contain less than or equal to 2% by weight, less than or equal to 1% by weight, or less than 0.5% by weight.

As an embodiment, the microparticles may be at least one of non-porous and porous. In the present specification, "non-porous" means that pores or voids are not included in the particle, and the surface porosity may be 0 or close to 0. As an example, the shape of the microparticles may be spherical or hemispherical, and may be bowl-shaped. Alternatively, the microparticles may include one or more of a spherical shape, a hemispherical shape and a bowl-shaped shape. In the present specification, the "bowl-shaped" is a concave bowl or barrel shape, and if the inside is hollow, it is not limited to the degree of depression or the shape of the bowl, and may be included. For example, the bowl-shape may have a shape of a round bowl with a recessed inside, more specifically, a half-spherical shape with a recessed inside. As an example, the microparticles included in the present invention may include bowl-shaped non-porous microparticles. In one embodiment, the bowl-shaped microparticles of the present invention may be non-porous. The bowl-shaped non-porous microparticles have better particle durability than conventional porous microparticles, and the poorly soluble bis-ethylhexyloxyphenol methoxyphenyl triazine can be very stably dispersed in the formulation.

In one embodiment, the size of the microparticles may have an average diameter of 1 to 10 μm, but bis-ethylhexyloxyphenol methoxyphenyl triazine is contained in a high content and can be stably dispersed in the composition formulation. The size is not limited thereto. The average diameter of the microparticles is an average value of particles included in the composition, and the average value of the particle diameter is a measurement of hydrodynamic volume under the assumption that the particles are spherical in the dispersed phase. Specifically, 30 ml of an isotone, Beckman Coulter solution was placed in a 100 ml container, a small amount of microparticles and a dispersant solution (10% of Triton X-100) were added to the container, and then the 150W sonicator was used. After dispersing the solution, the particle size was analyzed using Multisizer 4 (Beckman Coulter). The analysis results were expressed in units of one digit after the decimal point in Median (d(50) 3.5-5.5 μm). As a more specific embodiment, the average diameter of the microparticles is 1 μm or more, 2 μm or more, 3 μm or more, 4 μm or more, 5 μm or more, 6 μm or more, 7 μm or more, 8 μm or more, 9 μm or more, or 9.9 It may be more than μm, 10 μm or less, 9 μm or less, 8 μm or less, 7 μm or less, 6 μm or less, 5 μm or less, 4 μm or less, 3 μm or less, 2 μm or less, or 1.1 μm or less. Specifically, the average diameter of the microparticles may be 1 to 8 μm, more specifically 2 to 6 μm.

As an example, the bis-ethylhexyloxyphenol methoxyphenyl triazine contained in the microparticles may be evenly dispersed in a form close to a molecular unit without being crosslinked within a polymer matrix, specifically, a polymer crosslinked structure. Specifically, the bis-ethylhexyloxyphenol methoxyphenyl triazine is not crosslinked with the polymeric crosslinked structure inside the polymeric crosslinked structure of the polymer matrix, but is homogeneously mixed in a form close to the molecular unit in the net structure formed by the crosslinked structure, It may be dispersed and included, and other components included in the polymer matrix are not limited and all may be included as long as it is capable of producing microparticles. For example, the polymer matrix included in the bowl-shaped non-porous microparticles may include bis-ethylhexyloxyphenol methoxyphenyl triazine, and a polymer of a polymerizable monomer and a multifunctional crosslinking agent. More specifically, the microparticles may be prepared by dispersion polymerization using an oil phase containing all of bis-ethylhexyloxyphenol methoxyphenyl triazine, a polymerizable monomer, and a multifunctional crosslinking agent.

As an example, the microparticles may have different shapes depending on the ratio of bis-ethylhexyloxyphenol methoxyphenyl triazine contained therein. In view of the above, the bowl-shaped microparticles according to an embodiment may include bis-ethylhexyloxyphenol methoxyphenyl triazine in an amount of 20% to 30% by weight based on the total weight of the microparticles. More specifically, the particles contain bis-ethylhexyloxyphenol methoxyphenyl triazine based on the total weight of the microparticles in at least 20% by weight, at least 21% by weight, at least 22% by weight, at least 23% by weight, at least 24% by weight, 25% by weight or more, 26% by weight or more, 27% by weight or more, 28% by weight or more, 29% by weight or more, or 29.9% by weight or more, and 30% by weight or less, 29% by weight or less, 28% by weight or less , 27 wt% or less, 26 wt% or less, 25 wt% or less, 24 wt% or less, 23 wt% or less, 22 wt% or less, 21 wt% or less, or 20.1 wt% or less.

In one embodiment, the polymerizable monomer is a radical polymerizable monomer, and is not limited as long as it can be copolymerized with a polyfunctional crosslinking monomer, and specifically, may be a radical polymerizable monomer containing one ethylene group. For example, at least one aromatic vinyl monomer selected from the group consisting of styrene, methylstyrene, ethylstyrene, fluorostyrene, chlorostyrene and vinyltoluene; And methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate and glycidyl (meth) It may include one or more radical polymerizable monomers selected from the group consisting of one or more acrylic vinyl monomers selected from the group consisting of acrylates. As an example, the multifunctional crosslinking agent is not limited as long as it is a monomer capable of crosslinking the polymerizable monomer, and specifically, may be a crosslinking agent containing two or more ethylene groups. For example, divinylbenzene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylenepropane trimethacrylate, 1,3-butanediol dimethacrylate, 1 ,6-hexanedioldimethacrylate and tri(meth)acrylate may include one or more crosslinking agents selected from the group consisting of.

As an example, the polymer may be a methyl methacrylate crosspolymer formed by a radical polymerization reaction between methyl methacrylate and ethylene glycol dimethacrylate, and may have a random network structure.

As an example, the weight ratio of the polymerizable monomer and the multifunctional crosslinking agent may be changed without limitation according to a desired degree of crosslinking. For example, based on 100% by weight of the polymerizable monomer, the multifunctional crosslinking agent may be blended in an amount of 0.1 to 100% by weight, specifically 1 to 50% by weight, and more specifically, 1 to 25% by weight. have.

As an example, the composition may be a W/O (Water in Oil) type. Specifically, the composition may be W/S (Water in Silicon oil) type. In the present specification, the "W/S type" refers to an emulsion having a dispersed phase containing water in an oil containing silicone oil as a main component as a continuous phase. That is, the W/S type composition refers to an emulsion in a state in which an inner aqueous phase including water is dispersed in an outer oil phase including a silicone oil. The W/S type composition has a tendency to increase in preference due to its refreshing feeling, but the disadvantage that it cannot be applied to the W/S type composition is due to the very low solubility of bis-ethylhexyloxyphenol methoxyphenyl triazine itself in silicone oil. there was. Accordingly, the present invention solves the above problem by providing bis-ethylhexyloxyphenol methoxyphenyl triazine in the form of microparticles and dissolved in polar oil. In the present invention, bis-ethylhexyloxyphenol methoxyphenyl triazine can be applied to the above-described W/O-type or W/S-type trauma in a higher content than before.

The W/S type composition according to an embodiment of the present invention is dimethicone, cyclomethicone, phenyltrimethicone, polydimethylsiloxane, methylphenylpolysiloxane, methylcyclopolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dode One or two or more silicone oils selected from carmethylcyclohexasiloxane, tetradecamethylhexasiloxane, octamethyltrisiloxane, and the like may be included. As an embodiment, the silicone oil may be included in 15 to 60% by weight, specifically 15 to 50% by weight, more specifically 20 to 40% by weight based on the total weight of the composition, but limited thereto. It does not become. As an example, the composition may include a residual amount of water. In the W/S-type composition according to an embodiment of the present invention, the composition is a silicone-based surfactant containing at least one of polyethylene glycol (PEG), polypropylene glycol (PPG), and polyglyceryl group. It may be to further include. The composition according to an embodiment of the present invention stably disperses microparticles containing bis-ethylhexyloxyphenol methoxyphenyl triazine, and at the same time, bis-ethylhexyloxyphenol methoxyphenyl triazine precipitated as crystals on the interface. In terms of not generating azine, specifically, a silicone-based surfactant added with PEG may be used. Examples of PEG-added silicone surfactants include PEG/PPG-18/18 dimethicone (Cyclopentasiloxane and PEG/PPG-18/18 Dimethicone), PEG-30 dipolyhydroxystearate, and PEG-7 dimethicone. Chicone (PEG-7 Dimethicone), PEG-10 Dimethicone, Cyclopentasiloxane/ PEG.PPG-19.19 Dimethicone (Cyclopentasiloxane/PEG.PPG-19.19 Dimethicone), Sorbitan Isostearate (Sorbitan Isostearate) ), Lauryl PEG.PPG-18.18 Methicone (Lauryl PEG.PPG-18.18 Methicone), Cetyl PEG.PPG-10.1 Dimethicone (Cetyl PEG.PPG-10.1 Dimethicone), Lauryl PEG-9 Polydimethylsiloxyethyl Dimethicone Chicon (Lauryl PEG-9 Polydimethylsiloxyethyl Dimethicone), and the like. In addition, in the present invention, one or two or more PEG-added silicone-based surfactants may be used, but are not limited thereto. More specifically, the PEG-added silicone surfactant may be a nonionic surfactant having a hydrophilic-neophilic group balance (HLB) of 1 to 6. As an embodiment, the surfactant may be included in an amount of 0.01 to 10% by weight based on the total weight of the composition, specifically 1 to 8% by weight, more specifically 3 to 6% by weight. If it is less than 0.01% by weight, the dispersibility of the microparticles is deteriorated, and if it is more than 10% by weight, stickiness is caused, which may hinder a refreshing feeling of use.

The water-phase part of the W/S-type composition according to an embodiment of the present invention may include one or more of water and ethanol, and may include all components that may be included in the water-phase.

The composition according to the present invention is a cosmetic composition as an example, and may be formulated containing a cosmetically or dermatologically acceptable medium or base. These are all formulations suitable for topical application, such as solutions, gels, solids, dough anhydrous products, emulsions obtained by dispersing the oil phase in an aqueous phase, suspensions, microemulsions, microcapsules, microgranules or ionic (liposomes) and non It may be provided in the form of an ionic vesicle dispersant, or in the form of a cream, skin, lotion, powder, ointment, spray or conceal stick. It can also be used in the form of a foam or in the form of an aerosol composition further containing a compressed propellant. These compositions can be prepared according to conventional methods in the art.

As an embodiment of the present invention, the sun protection factor (SPF) of the composition may be 10 to 50, or more, as calculated by Equation 1 below. The UV A protection grade of UVA (PA) may be PA+ to PA++++.

[Equation 1]

UV protection index = (minimum amount of erythema in the skin area where the composition is applied)/ (minimum amount of erythema in the skin area where the composition is not applied)

In one embodiment, the composition may further include an organic sunscreen agent and an inorganic sunscreen agent depending on the purpose. The organic sunscreen or inorganic sunscreen may be included in an amount of 0.01 to 20% by weight, respectively, based on the total weight of the composition, but is not limited thereto. Specifically, organic sunscreens include octylmethoxycinnamate, octyl salicylate, octocrylene, butylmethoxydibenzoylmethane, oxybenzone, octyltriazone, menthylanthranylate, 3,4-methylbenzylidene camphor, Isoamyl-P-methoxycinnamate, methylenebisbenzotriazolitetramethylbutylphenol, and the like may be used, and powders such as titanium dioxide, zinc oxide, iron oxide, and zinc oxide may be used as the inorganic sunscreen.

As an example, the composition according to the present invention may contain, in addition to the active ingredient, other ingredients that can give a synergistic effect to the main effect within a range that does not impair the main effect. In addition to the ingredients, other ingredients may be appropriately selected and blended by a person skilled in the art according to the formulation or purpose of use of the other composition. In addition, as an example, the composition of the present invention may include the above ingredients and other ingredients that are usually blended in a cosmetic composition as needed. For example, moisturizers, emollients, thickeners, organic and inorganic pigments, organic powders, preservatives, fungicides, antioxidants, plant extracts, pH adjusters, alcohols, pigments, fragrances, blood circulation accelerators, cooling agents, limiting agents, And purified water. Other compounding ingredients that may be included in the composition of the present invention are not limited thereto, and the amount of the ingredients may be within a range not impairing the object and effect of the present invention.

Hereinafter, the present invention will be described in detail with reference to Examples, Comparative Examples and Test Examples. These are only illustratively presented to explain the present invention in more detail, and that the scope of the present invention is not limited by these Examples, Comparative Examples, and Test Examples, for those of ordinary skill in the art. It will be self-evident.

[Preparation Example 1] Preparation of microparticles containing bis-ethylhexyloxyphenol methoxyphenyl triazine

9 g of polyvinyl alcohol was added to the reaction tank and dissolved in 2000 g of distilled water to prepare an aqueous phase. 200 g of methyl methacrylate (MMA) and 25 g of ethylene glycol dimethacrylate were added to the emulsifier, stirred for 5 minutes, and 75 g of bis-ethylhexyloxyphenol methoxyphenyl triazine (BEMT) was added to dissolve for 30 minutes. To prepare an oil phase. Thus, 3 g of initiator 2,2'-azobis-(2,4-dimethylvaleronitrile was added and mixed. After the aqueous phase was added to the emulsifier, dispersion polymerization was performed for 30 minutes using an emulsifier, and the temperature was raised. Started and reacted for 15 hours at 50° C. After dehydration using a vacuum filter, washing with water three times and vacuum-dried, a bowl containing 25% by weight of the final bis-ethylhexyloxyphenol methoxyphenyl triazine- Polydisperse microparticles in the form of (Figs. 1A and 1B) were obtained (yield = 90%, average diameter of microparticles = 2 μm).

[Test Example 1] Bis-ethylhexyloxyphenol Methoxyphenyl Triazine Comparison of UV-blocking clinical results according to formulations

Microparticles comprising a polymer matrix in which bis-ethylhexyloxyphenol methoxyphenyl triazine is dispersed in an oil phase as an embodiment of the present invention; And bis-ethylhexyloxyphenol methoxyphenyl triazine (Tinosorb S®) dissolved in polar oil was prepared in the following composition. Specifically, bis-ethylhexyloxyphenol methoxyphenyl triazine (Tinosorb S®) was heated to 80°C in a polar oil, C12-C15 alkyl benzoate * titanium oxide * aluminum stearate * polyhydroxystearic acid * alumina. And completely dissolved, and then cooled. Components of the oil phase other than the above components were sequentially put into a container and mixed, and bis-ethylhexyloxyphenol methoxyphenyl triazine dissolved in the polar oil was put into a container containing the oil phase components, and uniformly dispersed and dissolved. After mixing and dissolving the components of the water phase in a separate container, it is emulsified using a homogenizer while putting it into a container containing the components of the oil phase, and the W/S type UV blocking composition of the sun milk formulation (Example 1 ) Was prepared.

The comparative example does not contain bis-ethylhexyloxyphenol methoxyphenyl triazine (Tinosorb S®) dissolved in polar oil, and the remaining oily components are sequentially added to silicone oils, except for dissolving and dispersing without heating. In the same manner as in Example 1, a sun milk formulation of a W/S type sunscreen composition (Example 1) was prepared.

Example 1 Comparative Example 1 Paid part Ethylhexylmethoxycinnamate*BHT 7 7 Ethylhexyl salicylate KSCI: octyl salicylate 4 4 Bis-ethylhexyloxyphenolmethoxyphenyltriazine (Tinosorb S®) One - Dimethicone 15 15 Cyclopentasiloxane*cyclohexasiloxane Balance Balance C12-15 alkyl benzoate* C12-15 alcohols 6 6 Disteadimonium hectorite 0.3 0.3 PEG-10 dimethicone 1.5 1.5 Tocopherol*lauryl PEG-9 polydimethylsiloxyethyl dimethicone 1.5 1.5 Preparation Example 1 (Bowl-shaped polydisperse microparticles containing 25% by weight of bis-ethylhexyloxyphenol methoxyphenyl triazine) 8 12 C12-C15 Alkyl benzoate*Titanium oxide*Aluminum stearate*Polyhydroxystearic acid*Alumina 5 5 Zinc oxide*hydrogendimethicone*PG-10 dimethicone*cyclopentasiloxane 11 11 Zinc oxide*triethoxycaprylylsilane 2.5 2.5 Award Distilled water 15 15 Polyol 5 5 Sodium chloride One One 2Na EDTA 0.05 0.05 antiseptic 1.15 1.15 ethanol 5 5 Total weight (% by weight) 100 100 Test result (n=3) Average SPF 41.1 Average SPF 22.6 Average PFA 8.1 Average PFA 7.7

Evaluation of the sun protection factor (SPF)

The amount of ultraviolet rays radiated from the solar simulater lamp to the test site was adjusted to 20-100mj/cm2 and irradiated on the back of the test subject. After 24 hours of irradiation with ultraviolet light, the minimum amount of erythema (Minimal Erythema Dosa: MED) was confirmed.

In order to confirm the UV-blocking effect of each sample (Example 1 and Comparative Example 1), 0.1 g of a sample was uniformly applied to the back of a subject in a thickness of 2 μl/cm 2, and left to stand for 15 minutes to dry. The UV irradiation window was attached to and fixed to each sample application area, and the other areas except the irradiation window were irradiated with UV rays while blocking UV rays using leather and towels.

Using the subject's MED as the standard (SPF 50), the amount of ultraviolet irradiation was irradiated, and the test was conducted by gradually increasing the amount of ultraviolet radiation. The minimum amount of erythema was determined after 24 hours of UV irradiation, and the UV blocking effect was calculated according to Equation 2 below, and is shown in Table 1 above.

[Equation 2]

UV protection index = (minimum amount of erythema in the skin area where the composition is applied)/(minimum amount of erythema in the skin area without the composition, MED)

Evaluation of sun protection factor (PFA)

The amount of ultraviolet A (320~400nm) radiated from the solar simulater lamp to the test site was adjusted to 6.40~19.54 J/cm ² and irradiated on the back of the test subject. After 24 hours of irradiation with ultraviolet A, the minimum persistent pigment darkening dose (MPPDD) was confirmed.

In order to confirm the UV A blocking effect of each sample (Example 1 and Comparative Example 1), 0.1 g of a sample was evenly applied to the back of a subject in a thickness of 2 μl/cm 2, left to stand for 15 minutes, and dried. The UV irradiation window was attached to and fixed to each sample application area, and the other areas except the irradiation window were irradiated with UV rays while blocking UV rays using leather and towels.

Using the subject's MPPDD as the standard (PFA 8), the amount of ultraviolet A irradiation was irradiated, and the test was conducted by gradually increasing the amount of ultraviolet A radiation. After 24 hours of UV A irradiation, the minimum sustained blackening amount was determined, and the UV A blocking effect was calculated according to Equation 3 below, and is shown in Table 1 above.

[Equation 3]

UV A blocking index = (minimum sustained blackening of the skin area to which the composition is applied)/(minimum sustained blackening of the skin area without the composition, MPPDD)

As a result, as shown in the table above, although Example 1 contained the same amount of bis-ethylhexyloxyphenol methoxyphenyl triazine than Comparative Example 1, the SPF index and PA index confirmed through clinical trials were the UV blocking power of Example 1. It can be seen that this is about two times higher, and the UV blocking effect of the present invention is excellent.

[Test Example 2] Bis-ethylhexyloxyphenol methoxyphenyl triazine stability comparison

The presence or absence of precipitation of bis-ethylhexyloxyphenol methoxyphenyl triazine according to the type of polar oil in the dissolved bis-ethylhexyloxyphenol methoxyphenyl triazine contained in the composition of the present invention was confirmed through the following experiment. If a polar oil capable of sufficiently dissolving bis-ethylhexyloxyphenol methoxyphenyl triazine is not included, bis-ethylhexyloxyphenol methoxyphenyl triazine precipitates, and thus it cannot function as a sunscreen.

In order to proceed with the experiment, the oil phase part of the W/S type composition was prepared with the composition shown in Table 2 below. At this time, the content of each component was described in weight% based on the total weight (100% by weight) of the composition including both the water phase and the oil phase. In this experiment, since a transparent oil phase is required to compare the solubility of bis-ethylhexyloxyphenol methoxyphenyl triazine, all powders including inorganic UV blockers that affect turbidity in the composition were excluded. Therefore, the total weight in the table below is 58% by weight. Specifically, bis-ethylhexyloxyphenol methoxyphenyl triazine (Tinosorb S®) was dissolved by heating at 80°C in ethylhexyl methoxycinnamate*BHT and ethylhexyl salicylate KSCI:octyl salicylate, and then cooled. I did. Components of the oil phase other than the above components were put into a container and mixed, and bis-ethylhexyloxyphenol methoxyphenyl triazine dissolved in the polar oil was put into a container containing the oil phase components, and uniformly dispersed and dissolved. Comparative Example 2 as a comparative example of the present invention was also prepared in the same manner as the above method.

Comparative Example 2 Example 2 Example 3 Example 4 Example 5 Paid part Trisiloxane*Dimethicone 5 2 2 2 3 Butylene glycol dicaprylate* dicapryate - 6 - - 3 C12-C15 alkyl benzoate - - 6 - - Dicaprylyl carbonate - - - 6 - Caprylyl Methicone*Phenyl Trimethicone 4 4 4 4 4 Diphenylsiloxy phenyl trimethicone 4 4 4 4 4 Dimethicone*trisiloxane 6 3 3 3 5 Trimethylsiloxysilicate*cyclopentasiloxane 3 3 3 3 3 ethanol 5 5 5 5 5 PEG-10 Dimethicone 1.5 1.5 1.5 1.5 1.5 Tocopherol*lauryl PEG-9 polydimethylsiloxyethyl dimethicone 2 2 2 2 2 Cyclopentasiloxane*cyclohexasiloxane Balance Balance Balance Balance Balance C12-C15 alkyl benzoate 4 4 4 4 4 Ethylhexyl methoxycinnamate*BHT 7 7 7 7 7 Ethylhexyl salicylate KSCI: octyl salicylate 4 4 4 4 4 Bis-ethylhexyloxyphenolmethoxyphenyltriazine (Tinosorb S®) 2 2 2 2 2 Total weight (% by weight) 58 58 58 58 58

While storing the prepared Comparative Examples 1 and 2 to 5 at room temperature, cold temperature (4°C) or frozen state, whether bis-ethylhexyloxyphenol methoxyphenyl triazine is precipitated, that is, stably dissolved in the oil phase is maintained. Was observed. Immediately after preparation, Examples 2 and 3 were relatively transparent, and the rest showed a semi-transparent state. At room temperature the next day, all were translucent except for Example 2. After 5 days at room temperature, Example 2 and Example 3 were transparent, but the rest were translucent. At the lapse of 3 weeks (week 4), all samples stored at room temperature were transparent and showed good stability (FIG. 3). Even after 7 weeks (week 8), all samples stored at room temperature were transparent and showed good stability (FIG. 5). In the samples stored at cold temperature from the next day, bis-ethylhexyloxyphenol methoxyphenyl triazine crystals precipitated in Comparative Example 2, and the remaining turbidity was formed in the order of Example 4> Example 3> Example 5> Example 2. Thus, it was found that Example 2 is the most excellent in stability (Fig. 2). As a result of freezing and thawing at 5 weeks after the 4 weeks elapsed cold storage sample, in Comparative Example 2, a large amount of bis-ethylhexyloxyphenol methoxyphenyl triazine crystals were precipitated, and Example 5 was bis- A small amount of ethylhexyloxyphenol methoxyphenyl triazine crystals precipitated. The turbidity of the remaining Examples 2 to 4 was similar to that of 3 weeks. In the case of samples stored frozen after 8 weeks (4 weeks cold and hot + 4 weeks frozen), the degree of precipitation of bis-ethylhexyloxyphenol methoxyphenyl triazine crystals was found in Comparative Example 2 >> Example 5> Example 4 and Example 2 > Example 3 appeared in the order (Fig. 4). A large amount of bis-ethylhexyloxyphenol methoxyphenyl triazine crystals precipitated in Comparative Example 2 in the case of the 9th week sample stored at room temperature by thawing after 8 weeks (4 weeks cold temperature + 4 weeks freezing), and in Example 5 bis -A small amount of ethylhexyloxyphenol methoxyphenyl triazine crystals precipitated (Fig. 6). 7 is a sample stored at room temperature for 1 year after the lapse of 8 weeks (4 weeks cold + 4 weeks frozen), and a large amount of bis-ethylhexyloxyphenol methoxyphenyl triazine crystals in Comparative Examples 2 and 5 Although this precipitated, in Examples 4, 2, and 3, precipitation did not appear even during long-term storage.

Taking the above results together, it can be seen that the stability of BEMT dissolved in the oil phase at room temperature after initial preparation is good, but differences between samples occur in BEMT solubility in refrigerated/frozen conditions. In addition to ethylhexyl methoxycinnamate and ethylhexyl salicylate used for dissolution in the initial oil phase, a certain amount of polar oil that can increase the solubility in the oil phase of BEMT must be added to secure the solubility in the oil phase of BEMT under various conditions. It means you can.

[Test Example 3] Skin stability evaluation

In order to check the skin stability of the composition according to an embodiment of the present invention, a patch test was performed on 18 adult women and 12 men (average 32.5 years old) with normal skin. Specifically, each composition of Example 1 and Comparative Example 1 prepared in Test Example 1 was directly contacted with the skin of the test subject through a patch, and then the patch was removed after 28 hours. The first reading was performed after 30 minutes and the second reading was performed after 96 hours. Table 3 below shows the secondary readout results, and in order to find out the intensity of skin irritation of Example 1 and Comparative Example 1, weights were assigned according to the degree of positive skin reaction to obtain the average skin reactivity and skin irritation of the sample. Was visually determined. At this time, the criterion is on a 5-point scale. If it is less than 1 point (grade I), no stimulation, 1 point or more and less than 3 points (grade II), light stimulation, 3 points or more and less than 5 points (grade III), medium stimulation, A score of 5 or higher (grade IV) was judged as a strong stimulation. The average skin reactivity was calculated according to the following equation.

[Equation 4]

Average reactivity Judgment grade Example 1 0 No irritation Comparative Example 1 0 No irritation

As a result, as shown in the table above, the composition according to an embodiment of the present invention was determined to have excellent skin safety.

The present invention can provide the following embodiments as an example.

In a first embodiment, microparticles comprising a polymer matrix including an aqueous phase and an oil phase, and in which bis-ethylhexyloxyphenol methoxyphenyl triazine (Bis-ethylhexyloxyphenol methoxyphenyl triazine) are dispersed in the oil phase; And bis-ethylhexyloxyphenol methoxyphenyl triazine dissolved in a polar oil, W/O (Water in Oil) type UV protection composition can be provided.

In the second embodiment, in the first embodiment, the microparticles may provide a composition, which is contained in an amount of 0.1 to 30% by weight based on the total weight of the composition.

The third embodiment is the bis-ethylhexyloxyphenol methoxyphenyl triazine of bis-ethylhexyloxyphenol methoxyphenyl triazine dissolved in the polar oil according to one or more of the first and second embodiments. Silver may provide a composition, which is contained in an amount of 0.01 to 2% by weight based on the total weight of the composition.

In a fourth embodiment, in one or more of the first to third embodiments, the polar oil is at least one of a carboxyl group (-COO), a ketone group (-CO), and a hydroxy group (-OH). It can provide a composition comprising an oil comprising a.

In a fifth embodiment, in one or more of the first to fourth embodiments, the polar oil is butylene glycol dicaprylate*dicapriate, ethylhexyl salicylate, ethylhexyl methoxycinnamate, homo Salate, C12-15 alkyl benzoate, dibutyl adipate, dicaprylyl carbonate, caprylyl-caprylate, cococaprylate, octocrylene, propylheptyl caprylate, isopropylpalmitate, capryl Compositions may be provided comprising oils of one or more of ric/capric triglycerides and cocoglycerides.

A sixth embodiment can provide a composition according to one or more of the first to fifth embodiments, wherein the microparticles are bowl-shaped non-porous microparticles.

In a seventh embodiment, according to one or more of the first to sixth embodiments, the microparticles contain bis-ethylhexyloxyphenol methoxyphenyl triazine in an amount of 20% to 30% by weight based on the total weight of the microparticles. It can provide a composition, including as.

The eighth embodiment can provide a composition in one or more of the first to seventh embodiments, wherein the average diameter of the microparticles is 1 to 10 μm.

The ninth embodiment, according to one or more of the first to eighth embodiments, wherein the polymer matrix comprises a polymer of bis-ethylhexyloxyphenol methoxyphenyl triazine, and a polymerizable monomer and a polyfunctional crosslinking agent. , Can provide a composition.

In a tenth embodiment, in one or more of the first to ninth embodiments, the polymerizable monomer is one selected from the group consisting of styrene, methylstyrene, ethylstyrene, fluorostyrene, chlorostyrene, and vinyltoluene. The above aromatic vinyl monomers; And methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate and glycidyl (meth) It is possible to provide a composition comprising at least one selected from the group consisting of at least one acrylic vinyl monomer selected from the group consisting of acrylate.

In the eleventh embodiment, in one or more of the first to tenth embodiments, the multifunctional crosslinking agent is divinylbenzene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, and triethylene glycol dimetha. Including one or more selected from the group consisting of acrylate, trimethylenepropane trimethacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, and tri(meth)acrylate, The composition can be provided.

In a twelfth embodiment, in one or more of the first to eleventh embodiments, the water-receiving part may provide a composition comprising at least one of water and ethanol.

The thirteenth embodiment can provide a composition in one or more of the first to twelfth embodiments, wherein the composition is a W/S (Water in Silicon oil) type.

Fourteenth embodiment can provide a composition according to one or more of the first to thirteenth embodiments, wherein the composition has a sun protection factor (SPF) of 30 or more.

Claims (14)

Including the award and the paid
Microparticles comprising a polymer matrix in which bis-ethylhexyloxyphenol methoxyphenyl triazine is dispersed in the oil phase; And bis-ethylhexyloxyphenol methoxyphenyl triazine dissolved in polar oil,
W/O (Water in Oil) type UV protection composition. The composition of claim 1, wherein the microparticles are contained in an amount of 0.1 to 30% by weight based on the total weight of the composition. The method of claim 1, wherein the bis-ethylhexyloxyphenol methoxyphenyl triazine of bis-ethylhexyloxyphenol methoxyphenyl triazine dissolved in the polar oil is contained in an amount of 0.01 to 2% by weight based on the total weight of the composition, Composition. The composition of claim 1, wherein the polar oil comprises an oil containing at least one polar functional group of a carboxyl group (-COO), a ketone group (-CO) and a hydroxy group (-OH). The method of claim 1, wherein the polar oil is butylene glycol dicaprylate*dicapriate, ethylhexyl salicylate, ethylhexyl methoxycinnamate, homosalate, C12-15 alkyl benzoate, dibutyl adipate, Dicaprylyl carbonate, caprylyl-caprylate, cococaprylate, octocrylene, propylheptyl caprylate, isopropyl palmitate, caprylic/capric triglyceride and cocoglyceride oil Comprising, a composition. The composition of claim 1, wherein the microparticles are bowl-shaped non-porous microparticles. The composition of claim 1, wherein the microparticles comprise bis-ethylhexyloxyphenol methoxyphenyl triazine in an amount of 20% to 30% by weight based on the total weight of the microparticles. The composition of claim 1, wherein the microparticles have an average diameter of 1 to 10 μm. The composition of claim 1, wherein the polymer matrix comprises a bis-ethylhexyloxyphenol methoxyphenyl triazine and a polymerizable product of a polymerizable monomer and a polyfunctional crosslinking agent. The method of claim 9, wherein the polymerizable monomer is at least one aromatic vinyl monomer selected from the group consisting of styrene, methylstyrene, ethylstyrene, fluorostyrene, chlorostyrene, and vinyltoluene; And methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate and glycidyl (meth) A composition comprising at least one selected from the group consisting of at least one acrylic vinyl monomer selected from the group consisting of acrylate. The method of claim 9, wherein the multifunctional crosslinking agent is divinylbenzene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylenepropane trimethacrylate, 1,3- Butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, and a composition comprising at least one selected from the group consisting of tri (meth) acrylate. The composition of claim 1, wherein the aqueous phase comprises at least one of water and ethanol. According to claim 1, wherein the composition is W / S (Water in Silicon oil) type, composition. The composition of claim 1, wherein the composition has a sun protection factor (SPF) of 30 or more.

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